Reinforced polyester compositions, method of manufacture, and articles thereof

ABSTRACT

A composition comprises, based on the total weight of the composition: from 20 to 90 wt. % of a polyester component comprising a modified poly(butylene terephthalate) copolymer that is derived from a poly(ethylene terephthalate) component; from 5 to 35 wt. % of a flame retardant phosphinate and/or a flame retardant diphosphinate; from 1 to 25 wt. % of a melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, and/or melamine phosphate; from greater than zero to 50 wt. % of a glass fiber having a non-circular cross-section; and from 0 to 5 wt. % of an additive.

BACKGROUND

This disclosure relates to polyester compositions, method ofmanufacture, and articles thereof.

Thermoplastic polyester compositions, such as poly(alkyleneterephthalates), have valuable characteristics including strength,toughness, high gloss, and solvent resistance. Polyesters therefore haveutility as materials for a wide range of applications, from automotiveparts to electric and electronic appliances. Because of their wide use,particularly in electronic applications, it is desirable to provideflame retardancy to polyesters.

Numerous flame retardants (FR) for polyesters are known, but manycontain halogens, usually chlorine and/or bromine. Halogenated flameretardant agents are less desirable because of the increasing demand forecologically friendly ingredients. Halogen-free flame retardants, suchas phosphorus- and nitrogen-based compounds can be used as well.Unfortunately, they lack good flame retardancy in thin sections.

More ecologically compatible flame retardant (eco-FR) formulations basedon aluminum salts of phosphinic or diphosphinic acid compounds andmelamine compounds have been developed to overcome environmental issuesof halogenated flame retardants. However, the formulations also possessundesirable mechanical properties, including reduced impact strength andtensile strength, as well as undesirable flow properties compared to thehalogenated flame retardant compositions.

An ongoing need exists for polyester compositions, particularly fromrecycled polyester, having the combination of good flame retardantproperties not only at thicknesses of 1.5 mm or greater, but also atthicknesses of 0.8 mm or less. It would be advantageous if thiscombination of flame retardant properties could be achieved while atleast essentially maintaining mechanical properties and/or heatproperties.

BRIEF SUMMARY OF THE INVENTION

A composition comprises based on the total weight of the composition:from 20 to 90 wt. % of a polyester component comprising a modifiedpoly(butylene terephthalate) copolymer, that (1) is derived from apoly(ethylene terephthalate) component selected from the groupconsisting of poly(ethylene terephthalate) and poly(ethyleneterephthalate) copolymers and (2) that has at least one residue derivedfrom the poly(ethylene terephthalate) component; from 5 to 35 wt. % of aflame retardant phosphinate of the formula (I)[(R¹)(R²)(PO)—O]⁻ _(m)M^(m+)  (I)a flame retardant diphosphinate of the formula (II)[(O—POR¹)(R³)(POR²—O)]²⁻ _(n)M^(m+) _(x)  (II),and/or a flame retardant polymer derived from the flame retardantphosphinate of the formula (I) or the flame retardant diphosphinate ofthe formula (II), wherein R¹ and R² are identical or different and areH, C₁-C₆ alkyl, linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀,alkylene, linear or branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, orC₇-C₁₁ arylalkylene; M is an alkaline earth metal, alkali metal, Al, Ti,Zn, Fe, or boron; m is 1, 2, 3 or 4; n is 1, 2, or 3; and x is 1 or 2;from 1 to 25 wt. % of a melamine polyphosphate, melamine cyanurate,melamine pyrophosphate, and/or melamine phosphate; from greater thanzero to 50 wt. % of a glass fiber having a non-circular cross-section;and from 0 to 5 wt. % of an additive selected from the group consistingof a mold release agent, an antioxidant, a thermal stabilizer, anantioxidant, and a UV stabilizer; wherein the components and have acombined total weight of 100 wt. %.

Also disclosed is a method for the manufacture of the composition,comprising blending the components of the composition.

Further disclosed are articles comprising the composition.

Methods of forming an article comprise shaping by extruding,calendaring, or molding the composition to form the article.

DETAILED DESCRIPTION OF THE INVENTION

Our invention is based on the discovery that it is now possible to makea thermoplastic polyester composition that includes a modifiedpoly(butylene terephthalate) copolymer that is made from post-consumeror post-industrial poly(ethylene terephthalate) (PET) and that has acombination of desirable flame retardance, thermal properties, andmechanical properties. Additionally, molded articles comprising thecomposition are less susceptible to warpage. The composition comprises apolyester component comprising a modified poly(butylene terephthalate)(PBT) derived from a post-consumer or post-industrial poly(ethyleneterephthalate) (PET); a nitrogen-containing flame retardant selectedfrom the group consisting of at least one of a triazine, a guanidine, acyanurate, an isocyanurate, and mixtures thereof; a phosphinic acid saltand/or diphosphinic acid salt and/or their polymers as described below;and a flat glass reinforcing fiber having a non-circular cross-section.The use of a modified polyester component in combination with a specificamount of a metal phosphinate salt, a particular nitrogen-containingflame retardant (melamine polyphosphate, melamine cyanurate, melaminepyrophosphate, and/or melamine phosphate), and a flat glass fiber,provides compositions that have excellent flame retardancy for boththick and thin articles, in the absence of a halogenated organic flameretardant. The compositions can further have very useful mechanicalproperties, in particular impact strength, tensile properties, and/orheat stability. The compositions can optionally comprise a charringpolymer, for example a polyetherimide, to further improve mechanicalstrength and flame retardance.

In a particularly advantageous feature, the polyester componentcomprises a modified poly(butylene terephthalate) component derived frompoly(ethylene terephthalate) (PET), for example waste PET soft drinkbottles. The modified PBT can also be referred to herein as PET-derivedPBT, PBT-IQ, or IQ-PBT. Unlike conventional molding compositionscontaining virgin PBT (PBT that is derived from monomers), the modifiedPBT component contains a poly(ethylene terephthalate) residue, e.g., amaterial such as ethylene glycol and isophthalic acid groups (componentsthat are not present in virgin, monomer-based PBT). Advantageously,despite using a PBT that is structurally different from virgin PBT, thecompositions and articles made from the composition described hereinexhibit similar performance properties as compositions and articles madefrom molding compositions containing monomer-based PBT. Use of modifiedPBT can provide a valuable way to effectively use underutilized scrapPET (from post-consumer or post-industrial streams) in PBT thermoplasticmolding compositions, thereby conserving non-renewable resources andreducing the formation of greenhouse gases, e.g., CO₂. Surprisingly,molding compositions containing modified-PBT copolymers derived frompoly(ethylene terephthalate) can exhibit improved flow properties, ascompared to molding compositions containing PBT derived from monomers.

As used herein the singular forms “a,” “an,” and “the” include pluralreferents. The term “combination” is inclusive of blends, mixtures,alloys, reaction products, and the like. Unless defined otherwise,technical and scientific terms used herein have the same meaning as iscommonly understood by one of skill. Compounds are described usingstandard nomenclature. The term “and a combination thereof” is inclusiveof the named component and/or other components not specifically namedthat have essentially the same function.

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, and the like, used in the specification and claims are to beunderstood as modified in all instances by the term “about.” Variousnumerical ranges are disclosed in this patent application. Because theseranges are continuous, they include every value between the minimum andmaximum values. The endpoints of all ranges reciting the samecharacteristic or component are independently combinable and inclusiveof the recited endpoint. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations. The term “from more than 0 to” an amount means that thenamed component is present in some amount more than 0, and up to andincluding the higher named amount.

All ASTM tests and data are from the 2003 edition of the Annual Book ofASTM Standards unless otherwise indicated. All cited references areincorporated herein by reference.

For the sake of clarity, the terms terephthalic acid group, isophthalicacid group, butanediol group, ethylene glycol group in formulas have thefollowing meanings. The term “terephthalic acid group” in a compositionrefers to a divalent 1,4-benzene radical (-1,4-(C₆H₄)—) remaining afterremoval of the carboxylic groups from terephthalic acid-. The term“isophthalic acid group” refers to a divalent 1,3-benzene radical(-(-1,3-C₆H₄)—) remaining after removal of the carboxylic groups fromisophthalic acid. The “butanediol group” refers to a divalent butyleneradical (—(C₄H₈)—) remaining after removal of hydroxyl groups frombutanediol. The term “ethylene glycol group” refers to a divalentethylene radical (—(C₂H₄)—) remaining after removal of hydroxyl groupsfrom ethylene glycol. With respect to the terms “terephthalic acidgroup,” “isophthalic acid group,” “ethylene glycol group,” “butane diolgroup,” and “diethylene glycol group” being used in other contexts,e.g., to indicate the weight % of the group in a composition, the term“isophthalic acid group(s)” means the group having the formula(—O(CO)C₆H₄(CO)—), the term “terephthalic acid group” means the grouphaving the formula (—O(CO)C₆H₄(CO)—), the term diethylene glycol groupmeans the group having the formula (—O(C₂H₄)O(C₂H₄)—), the term“butanediol group” means the group having the formula (—O(C₄H₈)—), andthe term “ethylene glycol groups” means the group having formula(—O(C₂H₄)—).

The residue derived from the poly(ethylene terephthalate) component,which is present in the modified poly(butylene terephthalate) componentcan be selected from the group consisting of ethylene glycol groups,diethylene glycol groups, isophthalic acid groups, antimony-containingcompounds, germanium-containing compounds, titanium-containingcompounds, cobalt-containing compounds, tin-containing compounds,aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers,1,4-cyclohexane dimethanol isomers, the cis isomer of 1,3-cyclohexanedimethanol, the cis isomer of 1,4-cyclohexane dimethanol, the transisomer of 1,3-cyclohexane dimethanol, the trans isomer of1,4-cyclohexane dimethanol, alkali salts, alkaline earth metal salts,including calcium, magnesium, sodium and potassium salts,phosphorous-containing compounds and anions, sulfur-containing compoundsand anions, naphthalene dicarboxylic acids, 1,3-propanediol groups, andcombinations thereof.

Depending on factors such as poly(ethylene terephthalate) andpoly(ethylene terephthalate) copolymers, the residue can include variouscombinations. For example, the residue can include mixtures of ethyleneglycol groups and diethylene glycol groups. The residue can also includemixtures of ethylene glycol groups, diethylene glycol groups, andisophthalic acid groups. The residue derived from poly(ethyleneterephthalate) can include the cis isomer of 1,3-cyclohexane dimethanolgroups, the cis isomer of 1,4-cyclohexane dimethanol groups, the transisomer of 1,3-cyclohexane dimethanol groups, the trans isomer of1,4-cyclohexane dimethanol groups, or combinations thereof. The residuecan also be a mixture of ethylene glycol groups, diethylene glycolgroups, isophthalic acid groups, cis isomer of cyclohexane dimethanolgroups, trans isomer of cyclohexane dimethanol groups, or combinationsthereof. The residue derived from poly(ethylene terephthalate) can alsoinclude mixtures of ethylene glycol groups, diethylene glycol groups,and cobalt-containing compounds. Such cobalt-containing compound mixturecan also contain isophthalic acid groups.

The amount of the ethylene glycol groups, diethylene glycol groups, andisophthalic groups in the polymeric backbone of the modified PBTcomponent can vary. The PET-derived modified PBT component ordinarilycontains isophthalic acid groups in an amount that is at least 0.1 mole% and can range from 0 or 0.1 to 10 mole % (0 or 0.07 to 7 wt. %). ThePET-derived modified PBT component ordinarily contains ethylene glycolin an amount that is at least 0.1 mole % and can range from 0.1 to 10mole % (0.02 to 2 wt. %). In one embodiment, the PET-derived modifiedPBT component has an ethylene glycol content that is more than 0.85 wt.%. In another embodiment, compositions can contain ethylene glycol in anamount from 0.1 wt. % to 2 wt. %. The modified PBT component can alsocontain diethylene glycol in an amount from 0.1 to 10 mole % (0.04 to 4wt. %). The amount of the butanediol groups is generally about 98 mole %and can vary from 95 to 99.8 mole % in some embodiments. The amount ofthe terephthalic acid groups is generally about 98 mole % and can varyfrom 90 to 99.9 mole % in some embodiments.

Unless otherwise specified, all molar amounts of the isophthalic acidgroups and/or terephthalic acid groups are based on the total moles ofdiacids/diesters in the composition. Unless otherwise specified, allmolar amounts of the butanediol, ethylene glycol, and diethylene glycolgroups are based on the total moles of diol in the composition. Theweight percent measurements stated above are based on the wayterephthalic acid groups, isophthalic acid groups, ethylene glycolgroups, and diethylene glycol groups have been defined herein.

The total amount of the poly(ethylene terephthalate) component residuein the modified poly(butylene terephthalate) copolymer can vary inamounts from 1.8 to 2.5 wt. %, or from 0.5 to 2 wt. %, or from 1 to 4wt. %, based on the total weight of the modified poly(butyleneterephthalate) copolymer. The ethylene glycol, diethylene glycol, andcyclohexane dimethanol groups can be present, individually or incombination, in an amount from 0.1 to 10 mole %, based on 100 mole % ofglycol in the molding composition. The isophthalic acid groups can bepresent in an amount from 0.1 to 10 mole %, based on 100 mole % ofdiacid/diester in the molding composition.

It has been discovered that when it is desirable to make a poly(butyleneterephthalate) copolymer having a melting temperature Tm that is atleast 200° C., the total amount of diethylene glycol, ethylene glycol,and isophthalic acid groups should be within a certain range. As such,the total amount of the diethylene glycol, ethylene glycol, andisophthalic acid groups in the modified poly(butylene terephthalate)component can be more than 0 and less than or equal to 23 equivalents,relative to the total of 100 equivalents of diol and 100 equivalents ofdiacid groups in the modified poly(butylene terephthalate) copolymer.The total amount of the isophthalic acid groups, ethylene glycol groups,and diethylene glycol groups can be from 3 to less than or equal to 23equivalents, relative to the total of 100 equivalents of diol and 100equivalents of diacid groups in the modified poly(butyleneterephthalate) copolymer. Alternatively, the total amount of theisophthalic acid groups, ethylene glycol groups, and diethylene glycolgroups can be from 3 to less than or equal to 10 equivalents, relativeto the total of 100 equivalents of diol and 100 equivalents of diacidgroups in the modified poly(butylene terephthalate) copolymer. Stillfurther, the total amount of the isophthalic acid groups, ethyleneglycol groups, and diethylene glycol groups can be from 10 to less thanor equal to 23 equivalents, relative to the total of 100 equivalents ofdiol and 100 equivalents of diacid groups in the modified poly(butyleneterephthalate) copolymer. The diethylene glycol, ethylene glycol, and/orisophthalic acid can be added during the process.

The total ethylene glycol groups, isophthalic acid groups, anddiethylene glycol groups can vary, depending on the application needs.The composition can have total monomer content selected from the groupconsisting of ethylene glycol, isophthalic acid groups, and diethyleneglycol groups in an amount from more than 0 and less than or equal to 17equivalents relative to the total of 100 equivalents of diol and 100equivalents of diacid groups in the modified poly(butyleneterephthalate) copolymer. Advantageously, such compositions can maintainuseful properties, such as heat deflection temperatures that are morethan 80° C.

It has also been discovered that the total amount of inorganic residuesderived from the poly(ethylene terephthalate) can be present from morethan 0 ppm and up to 1000 ppm. Examples of such inorganic residuesinclude those selected from the group consisting of antimony-containingcompounds, germanium-containing compounds, titanium-containingcompounds, cobalt-containing compounds, tin containing compounds,aluminum, aluminum salts, alkaline earth metal salts, alkali salts,including calcium, magnesium, sodium and potassium salts,phosphorous-containing compounds and anions, sulfur-containing compoundsand anions, and combinations thereof. The amounts of inorganic residuescan be from 250 to 1000 ppm, and more specifically from 500 to 1000 ppm.

The PET component from which the modified poly(butylene terephthalate)copolymer is made can have a variety of forms. Generally, the PETcomponent includes recycle (scrap) PET in flake, powder/chip, film, orpellet form. Before use, the PET is generally processed to removeimpurities such as paper, adhesives, polyolefin, e.g., polypropylene,polyvinyl chloride (PVC), nylon, polylactic acid, and othercontaminants. Also, the PET component can include PET that is not wastein flake, chip, or pellet form. As such, PET that would ordinarily bedeposited in landfills can now be used productively and effectively. ThePET component can also include other polyesters and/or polyestercopolymers. Examples of such materials include poly(alkyleneterephthalates) selected from the group consisting of poly(ethyleneterephthalate), poly(cyclohexane dimethanol terephthalate), copolyestersof terephthalate esters with comonomers containing cyclohexanedimethanoland ethylene glycol, copolyesters of terephthalic acid with comonomerscontaining cyclohexane dimethanol and ethylene glycol, poly(butyleneterephthalate), poly(xylylene terephthalate), poly(butyleneterephthalate), poly(trimethylene terephthalate), polyesternaphthalates, and combinations thereof.

The modified poly(butylene terephthalate) component derived frompoly(ethylene terephthalate) is (1) is derived from a poly(ethyleneterephthalate) component selected from the group consisting ofpoly(ethylene terephthalate) and poly(ethylene terephthalate) copolymersand (2) has at least one residue derived from the poly(ethyleneterephthalate) component. In one embodiment, the modified poly(butyleneterephthalate) component can further be derived from a biomass-derived1,4-butanediol, e.g. corn derived 1,4-butanediol or a 1,4-butanediolderived from a cellulosic material.

The modified poly(butylene terephthalate) copolymer can be derived fromthe poly(ethylene terephthalate) component by any method that involvesdepolymerization of the poly(ethylene terephthalate) component andpolymerization of the depolymerized poly(ethylene terephthalate)component with 1,4-butanediol to provide the modified poly(butyleneterephthalate) copolymer. For example, the modified poly(butyleneterephthalate) component can be made by a process that involvesdepolymerizing a poly(ethylene terephthalate) component selected fromthe group consisting of poly(ethylene terephthalate) and poly(ethyleneterephthalate) copolymers, with a 1,4-butanediol component at atemperature from 180° C. to 230° C., under agitation, at a pressure thatis at least atmospheric pressure in the presence of a catalystcomponent, at an elevated temperature, under an inert atmosphere, toproduce a molten mixture containing a component selected from the groupconsisting of oligomers containing ethylene terephthalate moieties,oligomers containing ethylene isophthalate moieties, oligomerscontaining diethylene terephthalate moieties, oligomers containingdiethylene isophthalate moieties, oligomers containing butyleneterephthalate moieties, oligomers containing butylene isophthalatemoieties, covalently bonded oligomeric moieties containing at least twoof the foregoing moieties, 1,4-butanediol, ethylene glycol, andcombinations thereof; and agitating the molten mixture atsub-atmospheric pressure and increasing the temperature of the moltenmixture to an elevated temperature under conditions sufficient to form amodified poly(butylene terephthalate) copolymer containing at least oneresidue derived from the poly(ethylene terephthalate) component.

Polyester moieties and the 1,4-butanediol are combined in the liquidphase under agitation and the 1,4-butanediol can be continuouslyrefluxed back into the reactor during step (a). The tetrahydrofuran(THF) and water formed in the stage can be removed by distillation orpartial condensation.

The poly(ethylene terephthalate) component and the 1,4-butanediolcomponent are generally combined under atmospheric pressure. In anotherembodiment, however, it is possible to use pressures that are higherthan atmospheric pressures. For instance, in one embodiment, thepressure at which the poly(ethylene terephthalate) component and the1,4-butanediol are subjected to is 2 atmospheres or higher. For higherpressures, the reaction mixtures can be depolymerized at temperatureshigher than 230° C.

The temperature at which the poly(ethylene terephthalate) component andthe 1,4-butanediol component are combined and reacted is sufficient topromote depolymerization of the poly(ethylene terephthalate) componentinto a mixture of oligomers containing ethylene terephthalate moieties,oligomers containing ethylene isophthalate moieties, oligomerscontaining diethylene terephthalate moieties, oligomers containingdiethylene isophthalate moieties, oligomers containing butyleneterephthalate moieties, oligomers containing butylene isophthalatemoieties, covalently bonded oligomeric moieties containing at least twoof the foregoing moieties, 1,4-butanediol, ethylene glycol, andcombinations thereof. The temperature at which the poly(ethyleneterephthalate) component and the 1,4-butanediol component are combinedgenerally ranges from 180 to 230° C. 1,4-Butanediol is generally used inexcess amount relative to the poly(ethylene terephthalate) component. Inone embodiment, 1,4-butanediol is used in a molar excess amount from 2to 20.

During the initial stage of the process when the poly(ethyleneterephthalate) component and the 1,4-butanediol are combined and react(“step (a)”), the poly(ethylene terephthalate) component and the1,4-butanediol depolymerize into a molten mixture at a pressure that isat least atmospheric pressure suitable conditions. 1,4-Butanediol andethylene glycol are generally recirculated, and tetrahydrofuran isdistilled during “step (a)” of the process. The molten mixture containsoligomers containing ethylene terephthalate moieties, oligomerscontaining ethylene isophthalate moieties, oligomers containingdiethylene terephthalate moieties, oligomers containing diethyleneisophthalate moieties, oligomers containing butylene terephthalatemoieties, oligomers containing butylene isophthalate moieties,covalently bonded oligomeric moieties containing at least two of theforegoing moieties, 1,4-butanediol, ethylene glycol, and combinationsthereof.

The duration of the step in which poly(ethylene terephthalate) componentreacts with 1,4-butanediol can vary, depending on factors, such asavailable equipment, production needs, desired final properties, and thelike. In one embodiment, this step is carried out in at least 2 hours.In another embodiment, the step is carried out from 2 to 5 hours.

The process further includes the step of subjecting the molten mixtureto sub-atmospheric pressure and increasing the temperature of the moltenmixture to a temperature from 240 to 260° C., and thereby forming themodified poly(butylene terephthalate) component derived from thepoly(ethylene terephthalate) component.

Excess butanediol, ethylene glycol, and THF are preferably removed andstep (b) is carried out under agitation. The molten mixture, when placedin sub-atmospheric pressure conditions at a suitable temperature for asufficiently long time period, polymerizes into a modified poly(butyleneterephthalate) component derived from the poly(ethylene terephthalate)component copolymer. Generally, the molten mixture pressure is subjectedto a pressure from sub-atmospheric to less than 1 Torr (0.133 MPa). Inone embodiment, the pressure is reduced to a pressure from 100 to 0.05Torr (13.3 to 0.0066 MPa) in a continuous manner. In another embodiment,the pressure is reduced to a pressure from 10 to 0.1 Torr (1.33 to0.0133 MPa) in a continuous fashion. Advantageously, the molten mixturecan be placed under sub-atmospheric conditions without isolation anddissolution of any material from the molten mixture. The avoidance ofthis step greatly enhances the utility of the process.

During the step when the molten mixture is placed under sub-atmosphericconditions and the temperature is increased, excess butanediol, ethyleneglycol, and THF are removed from the reactor and oligomers are allowedto build in molecular weight. Agitation can be continuously provided tofacilitate the removal of the low boiling components and allow themolecular weight buildup of the polymer. After sufficient molecularweight is obtained, the resulting molten PBT polymer is cast from thereactor through a diehead, cooled with water, stranded and chopped intopellets.

The duration of the step (step (b) discussed above) in which the moltenmixture polymerizes from poly(ethylene terephthalate) and poly(butyleneterephthalate) oligomers, 1,4-butanediol, and ethylene glycol can vary,depending on factors, such as equipment available, production needs,desired final properties, and the like. In one embodiment, this step iscarried out in at least two hours. In another embodiment, the step iscarried out from 2 to 5 hours.

The temperature at which the molten mixture is placed undersub-atmospheric conditions is sufficiently high to promotepolymerization of the poly(ethylene terephthalate) and poly(butyleneterephthalate) oligomers, 1,4-butanediol, and ethylene glycol to themodified poly(butylene terephthalate) component derived from thepoly(ethylene terephthalate) component. Generally, the temperature is atleast 230° C. In one embodiment, the temperature is from 250° C. to 275°C.

Both steps of the process can be carried out in the same reactor. In oneembodiment, however, the process is carried out in two separatereactors, where step (a) is carried out in a first reactor and when themolten mixture has formed, the molten mixture is placed in a secondreactor and step (b) is carried out. In another embodiment, the processcan be carried out in more than two reactors. In another embodiment, theprocess can be carried out in a continuous series of reactors.

The catalyst component that facilitates the reaction can be selectedfrom antimony compounds, tin compounds, titanium compounds, combinationsthereof as well as many other metal catalysts and combinations of metalcatalysts that have been disclosed in the literature. The amount of thecatalyst will vary depending on the specific need at hand. Suitableamounts of the catalyst range from 1 to 5000 ppm, or more. The catalystcomponent is generally added during the step when the poly(ethyleneterephthalate) component initially combines with the 1,4-butanediolcomponent. In another embodiment, however, the catalyst component can beadded to the molten mixture that forms after the poly(ethyleneterephthalate) component and the 1,4-butanediol component are combined.

The process for making the modified poly(butylene terephthalate)copolymer is preferably carried out under agitative conditions. The term“agitative conditions” or “agitation” refers to subjecting thepoly(ethylene terephthalate) component and the 1,4-butanediol or themolten mixture to conditions that involve physically mixing thepoly(ethylene terephthalate) component 1,4-butanediol or molten mixtureunder conditions that promote the depolymerization of the PET when theagitative conditions are applied to poly(ethylene terephthalate)component 1,4-butanediol, i.e., step (a), or the polymerization of thePBT from poly(ethylene terephthalate) oligomers, 1,4-butanediol, andethylene glycol, i.e., step (b). The physical mixing can be accomplishedby any suitable way. In one embodiment, a mixer containing rotatingshaft and blades that are perpendicular to the shaft can be used.

The process for making the modified poly(butylene terephthalate)copolymer can include a step that reduces the amount of THF producedduring the process by adding a basic compound containing an alkali metalto the reactor in step (a) and thereby reducing formation of THF. Thebasic compound contains an alkali metal and can be, for example, sodiumalkoxides, sodium hydroxide, sodium acetate, sodium carbonate, sodiumbicarbonates, potassium alkoxides, potassium hydroxide, potassiumacetate, potassium carbonate, potassium bicarbonate, lithium alkoxides,lithium hydroxide, lithium acetate, lithium carbonate, lithiumbicarbonate, calcium alkoxides, calcium hydroxide, calcium acetate,calcium carbonate, calcium bicarbonates, magnesium alkoxides, magnesiumhydroxide, magnesium acetate, magnesium carbonate, magnesiumbicarbonates, aluminum alkoxides, aluminum hydroxide, aluminum acetate,aluminum carbonate, aluminum bicarbonates, and combinations thereof. Theamount of the basic compound added to a mixture is generally at least0.1 ppm. In one embodiment, the amount of the basic compound is from 0.1to 50 ppm. In another embodiment, the amount of the basic compoundranges from 1 to 10 ppm.

In another embodiment, a difunctional epoxy compound can be added toreduce the formation of THF. The epoxy compounds can be selected fromthe group of difunctional epoxies. Examples of suitable difunctionalepoxy compounds include and are not limited to3,4-epoxycyclohexyl-3,4-epoxycyclohexyl carboxylate,bis(3,4-epoxycyclohexylmethyl)adipate, vinylcyclohexene di-epoxide,bisphenol diglycidyl ethers such as bisphenol-A diglycidyl ether,tetrabromobisphenol-A diglycidyl ether, glycidol, diglycidyl adducts ofamines and amides, diglycidyl adducts of carboxylic acids such as thediglycidyl ester of phthalic acid the diglycidyl ester ofhexahydrophthalic acid, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, butadiene diepoxide, vinylcyclohexene diepoxide,dicyclopentadiene diepoxide, and the like. Especially preferred is3,4-epoxycyclohexyl-3,4-epoxycyclohexylcarboxylate. The amount of theepoxy added to the mixture is generally at least 0.05 wt. %. In oneembodiment, the amount of the epoxy compound is from 0.1 to 1 wt. %. Inanother embodiment, the amount of the epoxy compound was 0.2 to 0.5 wt.%.

In another embodiment, THF production is reduced by a process thatinvolves the steps of: (a) reacting (i) a poly(ethylene terephthalate)component selected from the group consisting of poly(ethyleneterephthalate) and poly(ethylene terephthalate) copolymers with a diolcomponent selected from the group consisting of ethylene glycol,propylene glycol, and combinations thereof, in a reactor at a pressurethat is at least atmospheric pressure in the presence of a catalystcomponent at a temperature from 190° C. to 250° C., under an inertatmosphere, under conditions sufficient to depolymerize thepoly(ethylene terephthalate) component into a first molten mixturecontaining components selected from the group consisting of oligomerscontaining ethylene terephthalate moieties, oligomers containingethylene isophthalate moieties, oligomers containing diethyleneterephthalate moieties, oligomers containing diethylene isophthalatemoieties, oligomers containing trimethylene terephthalate moieties,oligomers containing trimethylene isophthalate moieties, covalentlybonded oligomeric moieties containing at least two of the foregoingmoieties, ethylene glycol, propylene glycol and combinations thereof;wherein the poly(ethylene terephthalate) component and the diolcomponent are combined under agitation; (b) adding 1,4-butanediol to thefirst molten mixture in a reactor in the presence of a catalystcomponent at a temperature from 190 to 240° C., under conditions thatare sufficient to form a second molten mixture containing a componentselected from the group consisting of oligomers containing ethyleneterephthalate moieties, oligomers containing ethylene isophthalatemoieties, oligomers containing diethylene terephthalate moieties,oligomers containing diethylene isophthalate moieties, oligomerscontaining trimethylene terephthalate moieties, oligomers containingtrimethylene isophthalate moieties, oligomers containing butyleneterephthalate moieties, oligomers containing butylene isophthalatemoieties, covalently bonded oligomeric moieties containing at least twoof the foregoing moieties, 1,4-butanediol, propylene glycol, ethyleneglycol, and combinations thereof; and (c) increasing the temperature ofthe second molten mixture under sub-atmospheric conditions and agitationto a temperature from 240 to 260° C., thereby forming a modifiedpoly(butylene terephthalate) copolymer containing at least one residuederived from the poly(ethylene terephthalate) component.

This three-step embodiment provides an additional advantageous way forproducing modified PBT copolymers from PET. The diol component used instep (a) of the three-step embodiment can be selected from ethyleneglycol, propylene glycol, and combinations thereof. The diol componentcan be present in step (a) at a molar amount that is at least half theamount of the ethylene glycol moieties present in the poly(ethyleneterephthalate) component. The depolymerization of the poly(ethyleneterephthalate) component can be carried out for various times. In oneembodiment, the depolymerization is carried out for at least 25 minutes.The 1,4-butanediol used during step (b) of the three step embodiment canbe added at a molar amount that is in excess relative to the molaramount of butanediol moieties incorporated into the modifiedpoly(butylene terephthalate) copolymer component obtained in step (c).During the process the compounds used in the process can be reusedand/or collected. In one embodiment, the diol component selected fromthe group consisting of ethylene glycol, propylene glycol, andcombinations thereof and (2) 1,4-butanediol are removed and collected ina vessel in step (b). In another embodiment, in step (b), 1,4-butanediolis refluxed back into the reactor and a component selected from thegroup of excess butanediol, ethylene glycol, propylene glycol,tetrahydrofuran, and combinations thereof is removed. Step (b) ispracticed for a sufficient period of time to reduce at least 65% ofethylene glycol from the second molten mixture. The duration of step (b)can also vary. In one embodiment, step (b) lasts at least 45 minutes.The pressure at which step (b) is carried out can vary. In oneembodiment, step (b) is carried out in atmospheric conditions. Inanother embodiment, step (b) is carried out in sub-atmosphericconditions. Different combinations are possible. In one embodiment, step(b) is carried out with excess 1,4-butanediol and at a pressure from 300to 1500 mbar absolute (30 to 150 MPa). In another embodiment,1,4-butanediol is used in a molar excess amount from 1.1 to 5. Step (c)of the three-step embodiment can also be carried out with modifications,depending on the application. In one embodiment, for example, acomponent selected from the group of excess butanediol, ethylene glycol,propylene glycol, tetrahydrofuran, and combinations thereof is removedduring step (c). The pressure at which step (c) is carried out can alsovary. In one embodiment, step (c) is carried out at a pressure that isless than 10 mbar (1 MPa). The three-step process can be carried out inthe same reactor. Alternatively, the three-step process can be carriedout in at least two reactors.

In another embodiment, the three-step process can include the step ofadding a basic compound during step (a), step (b), step (c), andcombinations thereof, and thereby further reduce THF production. Thebasic compound, as in the two-step embodiment, can contain thosecompounds mentioned above. Alternatively, difunctional epoxy compoundscan be added during step (b) in the amounts indicated above.

The process for making the modified PBT copolymer can contain anadditional step in which the PBT formed from the molten mixture issubjected to solid-state polymerization. Solid-state polymerizationgenerally involves subjecting the PBT formed from the molten mixture toan inert atmosphere or sub-atmospheric pressure and heating to atemperature for a sufficient period of time to build the molecularweight of the PBT. Generally, the temperature to which the PBT is heatedis below the melting temperature of the PBT, e.g., from 5° C. to 60° C.below the melting temperature of the PBT. In one embodiment, such atemperature can range from 150° C. to 210° C. Suitable periods of timeduring which the solid-state polymerization occurs can range from 2 to20 hours, depending on the conditions and equipment. The solid-statepolymerization is generally carried out under tumultuous conditionssufficient to promote further polymerization of the PBT to a suitablemolecular weight. Such tumultuous conditions can be created bysubjecting the PBT to tumbling, the pumping of inert gas into the systemto promote fluidization of polymer particle, e.g., pellets, chips,flakes, powder, and the like. The solid-state polymerization can becarried out at atmospheric pressure and/or under reduced pressure, e.g.from 1 atmosphere to 1 mbar (101 to 0.1 MPa).

In still another embodiment, the 1,4-butanediol used to make themodified poly(butylene terephthalate) copolymer can be derived frombiomass. The term “biomass” means living or dead biological matter thatcan be directly or subsequently converted to useful chemical substancesthat are ordinarily derived from non-renewable hydrocarbon sources.Biomass can include cellulosic materials, grains, starches derived fromgrains, fatty acids, plant based oils, as well as derivatives from thesebiomass examples. Examples of useful chemical substances include and arenot limited to diols; diacids; monomers used to make diols or acids,e.g., succinic acid; monomers used to make polymers; and the like.Biomass based butanediol can be obtained from several sources. Forinstance, the following process can be used to obtain biomass-based1,4-butanediol. Agriculture based biomass, such as corn, can beconverted into succinic acid by a fermentation process that alsoconsumes carbon dioxide. Such succinic acid is commercially availablefrom several sources such as from Diversified Natural Products Inc.under the trade name “BioAmber™.” This succinic acid can be easilyconverted into 1,4-butanediol by processes described in severalpublished documents such as in U.S. Pat. No. 4,096,156, incorporatedherein in its entirety. Bio-mass derived-1,4-butanediol can also beconverted to tetrahydrofuran, and further converted topolytetrahydrofuran, also known as poly(butylene oxide glycol). Smith etal. describe another process that describes converting succinic acidinto 1,4-butanediol in Life Cycles Engineering Guidelines, as describedin EPA publication EPA/600/R-1/101 (2001). When this embodiment is used,the manufacture of compositions containing the modified poly(butyleneterephthalate) can further reduce CO₂ emissions that are ordinarygenerated when PBT is made from fossil fuel derived monomers. Also, thisfurther reduces the amount of non-renewable hydrocarbon sources that areused in order to make the PBT.

The amount of the modified PBT copolymer in the compositions varies withthe specific application. Generally, the modified PBT copolymerfunctions as the polyester component of the composition. The polyestercomponent can accordingly comprise more than 0, up to 100 wt. % of themodified PBT copolymer, specifically from 1 to 99 wt. %, morespecifically from to 5 to 90 wt. %, even more specifically from 10 to 80wt. %, still more specifically from 20 to 70 wt. %, or from 30 to 60 wt.% Each of the foregoing is based on the total weight of the polyestercomponent.

The modified PBT copolymer can be combined with a second polyesterand/or polyester copolymer, for example virgin polyesters (polyestersderived from monomers rather than recycled polymer, including virginpoly(1,4-butylene terephthalate). More particularly, the secondpolyester can be obtained by copolymerizing a glycol component and adicarboxylic acid component comprising at least 70 mole %, morespecifically at least 80 mole %, of terephthalic acid, orpolyester-forming derivatives thereof. The glycol component, morespecifically tetramethylene glycol, can contain up to 30 mole %, morespecifically up to 20 mole % of another glycol, such as ethylene glycol,trimethylene glycol, 2-methyl-1,3-propane glycol, hexamethylene glycol,decamethylene glycol, cyclohexane dimethanol, neopentylene glycol,resorcinol, hydroquinone, and the like, and mixtures comprising at leastone of the foregoing glycols. The acid component can contain up to 30mole %, more specifically up to 20 mole %, of another acid such asisophthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,5-naphthalene dicarboxylic acid, 4,4′-diphenyldicarboxylic acid, 4,4′-diphenoxyethanedicarboxylic acid, sebacic acid,adipic acid, 4,4′-dicarboxydiphenyl ether,1,2-di(p-carboxyphenyl)ethane, and the like, and polyester-formingderivatives thereof, and mixtures comprising at least one of theforegoing acids or acid derivatives. Most specifically, the dicarboxylicacid is selected from the group consisting of terephthalic acid,isophthalic acid, naphthalene dicarboxylic acids, and the like, andmixtures comprising at least one of the foregoing dicarboxylic acids.

Also contemplated herein are second polyesters comprising minor amounts,e.g., 0.5 to 30 percent by weight, of units derived from aliphatic acidsand/or aliphatic polyols to form copolyesters. The aliphatic polyolsinclude glycols, such as poly(ethylene glycol). Such polyesters can bemade following the teachings of, for example, U.S. Pat. No. 2,465,319 toWhinfield et al., and U.S. Pat. No. 3,047,539 to Pengilly.

Second polyesters comprising block copolyester resin components are alsocontemplated, and can be prepared by the transesterification of (a)straight or branched chain poly(alkylene terephthalate) and (b) acopolyester of a linear aliphatic dicarboxylic acid and, optionally, anaromatic dibasic acid such as terephthalic or isophthalic acid with oneor more straight or branched chain dihydric aliphatic glycols.Especially useful when high melt strength is important are branched highmelt viscosity resins, which include a small amount of, e.g., up to 5mole percent based on the acid units of a branching component containingat least three ester forming groups. The branching component can be onethat provides branching in the acid unit portion of the polyester, inthe glycol unit portion, or it can be a hybrid branching agent thatincludes both acid and alcohol functionality. Illustrative of suchbranching components are tricarboxylic acids, such as trimesic acid, andlower alkyl esters thereof, and the like; tetracarboxylic acids, such aspyromellitic acid, and lower alkyl esters thereof, and the like; orpreferably, polyols, and especially preferably, tetrols, such aspentaerythritol; triols, such as trimethylolpropane; dihydroxycarboxylic acids; and hydroxydicarboxylic acids and derivatives, such asdimethyl hydroxyterephthalate, and the like. Branched poly(alkyleneterephthalate) resins and their preparation are described, for example,in U.S. Pat. No. 3,953,404 to Borman. In addition to terephthalic acidunits, small amounts, e.g., from 0.5 to 15 mole percent of otheraromatic dicarboxylic acids, such as isophthalic acid or naphthalenedicarboxylic acid, or aliphatic dicarboxylic acids, such as adipic acid,can also be present, as well as a minor amount of diol component otherthan that derived from 1,4-butanediol, such as ethylene glycol orcyclohexane dimethanol, etc., as well as minor amounts of trifunctional,or higher, branching components, e.g., pentaerythritol, trimethyltrimesate, and the like.

More specific second polyesters include those selected from the groupconsisting of poly(ethylene terephthalate), poly(1,4-butyleneterephthalate), poly(ethylene naphthalate), poly(1,4-butylenenaphthalate), poly(trimethylene terephthalate),poly(1,4-cyclohexanenedimethylene 1,4-cyclohexanedicarboxylate),poly(1,4-cyclohexanedimethylene terephthalate),poly(1,4-butylene-co-1,4-but-2-ene diol terephthalate),poly(cyclohexanedimethylene-co-ethylene terephthalate), and acombination thereof. Most specifically, the second polyester is virginpoly(1,4-butylene terephthalate).

However, in a specific embodiment, the polyester component of thethermoplastic composition consists essentially of the modifiedpoly(1,4-butylene terephthalate), such that the presence of any otherpolymer resins (e.g., a second polyester, a polycarbonate, or apolycarbonate-polyester) do not significantly adversely affect the basisand novel properties of the composition. A polymer species such as animpact modifier or anti-drip agent, can accordingly be present. Inanother embodiment, the polyester component contains only the modifiedpoly(1,4-butylene terephthalate), such that the thermoplasticcompositions have no other polyester, polycarbonate, orpolycarbonate-ester, other than the modified poly(1,4-butyleneterephthalate). Again, a polymer species such as an impact modifier oranti-drip agent, can be present, because these species are not part ofthe polyester component as defined herein.

Any of the foregoing first and optional second polyesters can have anintrinsic viscosity of 0.4 to 2.0 deciliters per gram (dL/g), measuredin a 60:40 by weight phenol/1,1,2,2-tetrachloroethane mixture at 23° C.The PBT can have a weight average molecular weight of 10,000 to 200,000Daltons, specifically 50,000 to 150,000 Daltons as measured by gelpermeation chromatography (GPC). The polyester component can alsocomprise a mixture of different batches of PBT prepared under differentprocess conditions in order to achieve different intrinsic viscositiesand/or weight average molecular weights.

The polyester component comprising the modified PBT can be present inthe composition in an amount from 20 to 90 weight percent, based on thetotal weight of the composition. Within this range, it is preferred touse at least 25 weight percent, even more preferably at least 30 weightpercent of the polyester component. In one embodiment, the polyestercomponent is present in an amount of 20 to 80 weight percent, based onthe total weight of the composition, specifically 35 to 75 weightpercent, even more specifically 40 to 75 weight percent, each based onthe total weight of the composition.

The composition includes a flame retarding quantity of one or a mixtureof nitrogen-containing flame retardants such as triazines, guanidines,cyanurates, and isocyanurates. Preferred triazines have the formula:

wherein R²⁵, R²⁶, and R²⁷ are independently C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy,C₆-C₁₂ aryl, amino, C₁-C₁₂ alkyl-substituted amino, or hydrogen. Highlypreferred triazines include 2,4,6-triamine-1,3,5-triazine (melamine, CASReg. No. 108-78-1), melamine derivatives, melam, melem, melon, ammeline(CAS Reg. No. 645-92-1), ammelide (CAS Reg. No. 645-93-2),2-ureidomelamine, acetoguanamine (CAS Reg. No. 542-02-9), benzoguanamine(CAS Reg. No. 91-76-9), and the like. Salts/adducts of these compoundswith boric acid or phosphoric acid can be used in the composition.Examples include melamine pyrophosphate and melamine polyphosphate.Preferred cyanurate/isocyanurate compounds include salts/adducts of thetriazine compounds with cyanuric acid, such as melamine cyanurate andany mixtures of melamine salts.

Preferred guanidine compounds include guanidine; aminoguanidine; and thelike; and their salts and adducts with boric acid, carbonic acid,phosphoric acid, nitric acid, sulfuric acid, and the like; and mixturescomprising at least one of the foregoing guanidine compounds.

The nitrogen-containing flame retardant can be present in thecomposition at 1 to 25 weight percent, based on the total weight of thecomposition. Within this range, it is preferred to use at least 5 weightpercent, even more preferably at least 8 weight percent of thenitrogen-containing flame retardant. Also within this range, it ispreferred to use up to 20 weight percent.

In a specific embodiment, it has been found advantageous to use from 1to 25 wt. % of a melamine polyphosphate, melamine cyanurate, melaminepyrophosphate, and/or melamine phosphate, based on the total weight ofthe composition. Particularly good results are obtained using from 1 to25 wt. % of a melamine polyphosphate and/or melamine cyanurate,specifically 8 to 20 wt. % of melamine polyphosphate and/or melaminecyanurate, based on the total weight of the composition.

The nitrogen-containing flame-retardants are used in combination withone or more phosphinic acid salts. The phosphinates and diphosphinatesinclude those set forth in U.S. Pat. No. 6,255,371 to Schosser et al.The specification of this patent, column 1, line 46 to column 3 line 4is incorporated by reference into the present specification. Specificphosphinates mentioned include aluminum diethylphosphinate (DEPAL), andzinc diethylphosphinate (DEPZN). The phosphinates have the formula (I)[(R¹)(R²)(PO)—O]_(m) ⁻M^(m+) and formula II [(O—POR¹)(R³)(POR²—O)]²⁻_(n)M^(m+) _(x), and/or polymers comprising such formula I or II,wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl,linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linearor branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁arylalkylene; M is an alkaline earth metal, alkali metal, Al, Ti, Zn,Fe, or boron; m is 1, 2, 3 or 4; n is 1, 2, or 3; and x is 1 or 2. Inone embodiment R¹ and R² are the same and are C₁-C₆-alkyl, linear orbranched, or phenyl; R³ is C₁-C₁₀-alkylene, linear or branched,C₆-C₁₀-arylene, -alkylarylene or -arylalkylene; M is magnesium, calcium,aluminum, zinc, or a combination thereof; m is 1, 2 or 3; n is 1, 2 or3; and x is 1 or 2. The structures of formula I and II are specificallyincorporated by reference from the Schosser patent into the presentapplication. Note that R¹ and R² can be H, in addition to thesubstituents referred to set forth in the patent. This results in ahypophosphite, a subset of phosphinate, such as calcium hypophosphite,aluminum hypophosphite, and the like.

In a specific embodiment M is aluminum, and the composition comprisesfrom 5 to 35 wt. %, specifically from 7 to 20 wt. % of a flame retardantphosphinate of the formula (Ia)[(R¹)(R²)(PO)—O]⁻ ₃Al³⁺  (Ia),a flame retardant diphosphinate of the formula (IIa)[(O—POR¹)(R³)(POR²—O)]²⁻ ₃Al³⁺ ₂  (IIa),and/or a flame retardant polymer comprising formula (Ia) or (IIa),wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl,linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linearor branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁arylalkylene.

The molding composition also comprises from greater than zero to about50 wt. %, based on the weight of the entire composition, of areinforcing fiber having a non-circular cross-section. Any rigid fibercan be used, for example, glass fibers, carbon fibers, metal fibers,ceramic fibers or whiskers, and the like. In particular flat glassfibers are employed in an amount from about 10 wt. % to about 40 wt. %,or about 10 wt. % to about 30 wt. % based on the weight of the entirecomposition. Preferred flat glass fibers typically have a modulus ofgreater than or equal to about 6,800 megaPascals, and can be chopped orcontinuous. The flat glass fiber can have various cross-sections, forexample, trapezoidal, rectangular, or square, crescent, bilobal,trilobal, and hexagonal.

In preparing the molding compositions it is convenient to use a glassfiber in the form of chopped strands having an average length of from0.1 mm to 10 mm, and having an average aspect ratio of 2 to 5. Inarticles molded from the compositions on the other hand shorter lengthswill typically be encountered because during compounding considerablefragmentation can occur.

In some applications it can be desirable to treat the surface of thefiber with a chemical coupling agent to improve adhesion to athermoplastic resin in the composition. Examples of useful couplingagents are alkoxy silanes and alkoxy zirconates. Amino, epoxy, amide, orthio functional alkoxy silanes are especially useful. Fiber coatingswith high thermal stability are preferred to prevent decomposition ofthe coating, which could result in foaming or gas generation duringprocessing at the high melt temperatures required to form thecompositions into molded parts. In one embodiment, no round glass fibersare present in the compositions. In another embodiment, only a flatglass fiber is present as a filler component.

In still other embodiments, the compositions can additionally comprise anon-fibrous inorganic filler, which can impart additional beneficialproperties to the compositions such as thermal stability, increaseddensity, stiffness, and/or texture. Typical non-fibrous inorganicfillers include, but are not limited to, alumina, amorphous silica,alumino silicates, mica, clay, talc, glass flake, glass microspheres,metal oxides such as titanium dioxide, zinc sulfide, ground quartz, andthe like. In various embodiments the amount of non-fibrous filler can bein a range of between about 1 wt. % and about 50 wt. % based on theweight of the entire composition.

In some embodiments, combinations of glass fibers, carbon fibers, orceramic fibers with a flat, plate-like filler, for example mica orflaked glass, can give enhanced properties. Typically, the flat,plate-like filler has a length and width at least ten times greater thanits thickness, where the thickness is from 1 to about 1000 microns.Combinations of rigid fibrous fillers with flat, plate-like fillers canreduce warp of the molded article.

In one embodiment, the fibrous reinforcing filler consists essentiallyof flat glass fibers. In another embodiment, the fibrous reinforcingfiller consists of flat glass fibers, i.e., the only fibrous reinforcingfiller present is the flat glass fibers.

The molding composition can optionally comprise a charring polymer. Acharring polymer is a polymer that has not more than 85% weight loss at400° C. to 500° C. upon heating under nitrogen using a thermogravimetricanalysis (TGA) at a heating rate of 20° C. per minute. Typical charringpolymers include polyetherimides, poly(phenylene ether),poly(phenylenesulfide), polysulphones, polyethersulphones,poly(phenylenesulphide oxide) (PPSO), and polyphenolics (e.g.,novolacs). The charring polymer can be present in an amount from 0.1 to15 percent by weight of the composition. In a specific embodiment, apolyetherimide is used, specifically an aromatic polyetherimide. Whenpresent, the polyetherimide can be present in an amount from more than 0to 25 wt. %, specifically 0.1 to 25 wt. %, even more specifically from 2to 8 wt. %, each based on the total weight of the composition. Thepresence of a polyetherimide in compositions comprising aluminumphosphinate salts can further improve the mechanical properties of thecompositions, in particular tensile strength and impact properties. Hightemperature molding stability can also be further improved, as well asmelt stability. In one embodiment, the composition includes more than 0to less than 10 wt % of a polyetherimide, based on the total weight ofthe composition. In a unique advantage of the current compositions,improvement in flexural modulus, notched and unnotched Izod impactstrength, tensile stress at break and/or elastic modulus is observedwhen the composition comprises no charring polymer, in particular nopolyetherimide.

The composition can further comprise one or more anti-dripping agents,which prevent or retard the resin from dripping while the resin issubjected to burning conditions. Specific examples of such agentsinclude silicone oils, silica (which also serves as a reinforcingfiller), asbestos, and fibrillating-type fluorine-containing polymers.Examples of fluorine-containing polymers include fluorinated polyolefinssuch as, for example, poly(tetrafluoroethylene),tetrafluoroethylene/hexafluoropropylene copolymers,tetrafluoroethylene/ethylene copolymers, poly(vinylidene fluoride),poly(chlorotrifluoroethylene), and the like, and mixtures comprising atleast one of the foregoing anti-dripping agents. A preferredanti-dripping agent is poly(tetrafluoroethylene) encapsulated by astyrene: acrylonitrile (SAN) copolymer. When used, an anti-drippingagent is present in an amount of 0.02 to 2 weight percent, and morepreferably from 0.05 to 1 weight percent, based on the total weight ofthe composition.

With the proviso that flame retardance properties and mechanicalproperties such as impact strength, tensile modulus and flexural modulusare not adversely affected, the compositions may, optionally, furthercomprise other conventional additives used in polyester polymercompositions such as non-reinforcing fillers, stabilizers such asantioxidants, thermal stabilizers, radiation stabilizers, andultraviolet light absorbing additives, mold release agents,plasticizers, quenchers, lubricants, antistatic agents and processingaids. Other ingredients, such as dyes, pigments, laser markingadditives, and the like can be added for their conventionally employedpurposes. A combination comprising one or more of the foregoing or otheradditives can be used.

In an advantageous feature, the composition possesses good flameretardancy substantially in the absence of a halogenated, in particulara chlorinated and/or brominated organic flame retardant compound. In oneembodiment, the compositions comprise 0 to 5 wt. % of a chlorinatedand/or brominated organic compound. In another embodiment, thecompositions comprise 0 to less than 3 wt. % of a chlorinated and/orbrominated organic compound. In still another embodiment, thecompositions comprise less than 2000 ppm, less than 500 ppm, or lessthan 100 ppm of a chlorinated and/or brominated organic flame retardantcompound.

Where it is important to make compositions having a light grey or awhite appearance, a composition can further include a mixture of zincsulfide and zinc oxide in sufficient amounts to produce a compositionhaving a light grey appearance or a white appearance. The specificamounts of mixtures of zinc sulfide and zinc oxide can vary, dependingon the application. In one embodiment, the zinc sulfide is present in anamount that is at least 3 weight percent, based on the total weight ofthe composition. In another embodiment, the zinc oxide is present in anamount that is at least 0.05 weight percent, based on the total weightof the composition. In another embodiment, the zinc sulfide is presentin an amount ranging from 3 to 14 weight percent, based on the totalweight of the composition. In another embodiment, the zinc oxide ispresent in an amount ranging from 0.05 to 14 weight percent, based onthe total weight of the composition. The light gray or white compositioncan have LAB values that can vary. As further discussed below, the useof the mixture of zinc sulfide and zinc oxide produces a material oflight gray or white appearance that does not emit an unpleasant odorthat results from the formation of hydrogen sulfide.

The compositions can be prepared by blending the components of thecomposition, employing a number of procedures. In an exemplary process,the polyester component, phosphorous flame retardant, melaminecomponent, glass fiber, and optional additives are put into an extrusioncompounder with resinous components to produce molding pellets. Theresins and other ingredients are dispersed in a matrix of the resin inthe process. In another procedure, the ingredients and any reinforcingglass are mixed with the resins by dry blending, and then fluxed on amill and comminuted, or extruded and chopped. The composition and anyoptional ingredients can also be mixed and directly molded, e.g., byinjection or transfer molding techniques. Preferably, all of theingredients are freed from as much water as possible. In addition,compounding should be carried out to ensure that the residence time inthe machine is short; the temperature is carefully controlled; thefriction heat is utilized; and an intimate blend between the resincomposition and any other ingredients is obtained.

Preferably, the ingredients are pre-compounded, pelletized, and thenmolded. Pre-compounding can be carried out in conventional equipment.For example, after pre-drying the polyester composition (e.g., for fourhours at 120° C.), a single screw extruder can be fed with a dry blendof the ingredients, the screw employed having a long transition sectionto ensure proper melting. Alternatively, a twin screw extruder withintermeshing co-rotating screws can be fed with resin and additives atthe feed port and reinforcing additives (and other additives) can be feddownstream. In either case, a generally suitable melt temperature willbe 230° C. to 300° C. The pre-compounded composition can be extruded andcut up into molding compounds such as conventional granules, pellets,and the like by standard techniques. The composition can then be moldedin any equipment conventionally used for thermoplastic compositions,such as a Newbury or van Dorn type injection molding machine withconventional cylinder temperatures, at 230° C. to 280° C., andconventional mold temperatures at 55° C. to 95° C. The moldedcompositions provide an excellent balance of impact strength and flameretardancy.

In embodiments where the compositions are of a light grey or a whitecolor, a composition can be made by a method that includes a method forthe manufacture of a composition, which comprises blending thecomponents of the composition and further includes that step of adding amixture of zinc sulfide and zinc oxide in sufficient amounts (i) toproduce a composition having a light grey or white appearance and (ii)to inhibit formation of hydrogen sulfide. Hydrogen sulfide emits anhighly undesirable odor and inhibiting the formation of such gas makesthe use of such a material highly useful. In one embodiment, the zincsulfide is present in an amount ranging from 3 to 14 weight percent,based on the total weight of the composition. In another embodiment, thezinc oxide is present in an amount ranging from 0.05 to 14 weightpercent, based on the total weight of the composition.

In particular, the compositions provide excellent flame retardancy whenmolded into either thick or thin components. One set of test conditionscommonly accepted and used as a standard for flame retardancy is setforth in Underwriters Laboratories, Inc. Bulletin 94, which prescribescertain conditions by which materials are rated for self-extinguishingcharacteristics. Another set of conditions commonly accepted and used(especially in Europe) as a standard for flame retardancy is the GlowWire Ignition Test (GWIT), performed according to the Internationalstandard IEC 695-2-1/2. A 0.8 mm thick molded sample comprising thecomposition can have a UL-94 flammability rating of V0. A 0.4 mm thickmolded sample comprising the composition can also have a UL-94flammability rating of V0.

A molded article comprising the composition has a melting viscosity offrom 200 to 400 Pa·s, measured in accordance with ISO11443 at 250° C.and a shear rate of 645 l/s. The melting viscosity can be at least 5%lower than for the same composition having the same amount of circularglass fibers, each measured at 250° C. in accordance with ISO11443.

A molded article comprising the composition can have a flexural modulusof from 3000 MPa to 20000 MPa, measured in accordance with ASTM 790, andthe flexular stress at break can be from 120 to 200 MPa, morespecifically 130 to 190 MPa, measured in accordance with ASTM 790.

A molded article comprising the composition can have good impactproperties, for example, an unnotched Izod impact strength from to 300to 700 J/m, measured at 23° C. in accordance with ASTM D256. Theunnotched Izod impact strength can be at least 20% higher than for thesame composition having the same amount of circular glass fibers, eachmeasured at 23° C. in accordance with ASTM D256.

A molded article comprising the composition can have a notched Izodimpact strength from to 50 to 80 J/m, measured at 23° C. in accordancewith ASTM D256. The notched Izod impact strength can be at least 3%higher than for the same composition having the same amount of circularglass fibers, each measured at 23° C. in accordance with ASTM D256.

A molded article comprising the composition can have a heat deflectiontemperature from 195° C. to 225° C., measured in accordance with ASTMD648 at 1.8 MPa.

The composition can further have good tensile properties. A moldedarticle comprising the composition can have a tensile modulus ofelasticity from 2000 MPa to 15000 MPa, measured in accordance with ASTM790. A molded article comprising the composition can have a tensileelongation at break from 1 to 3%, measured in accordance with ASTM 790.A molded article comprising the composition can have a tensile stress atbreak from to 80 to 150 MPa, measured in accordance with ASTM 790.

The compositions also exhibit less warpage. A molded article comprisingthe composition has a warpage of from 5 to 20 mm, measured at 23° C. asmolded. The warpage can be at least 20% lower than for the samecomposition having the same amount of circular glass fibers, eachmeasured at 23° C. as molded. Further, a molded article comprising thecomposition has a warpage of from 5 to 20 mm, measured after beingannealed at 70° C. for 48 Hrs. The warpage can be at least 15% lowerthan for the same composition having the same amount of circular glassfibers, each measured after being annealed at 70° C. for 48 Hrs.

In a specific embodiment, the compositions can have a combination ofhighly useful physical properties. For example, a molded articlecomprising the composition can have an unnotched Izod impact strength ofequal to 300 to 700 J/m, measured at 23° C. in accordance with ASTM D256and a heat deflection temperature from 195° C. to 225° C., measured inaccordance with ASTM D648 at 1.82 MPa; and a 0.8 mm thick molded samplecomprising the composition can have a UL-94 flammability rating of V0.

One or more of the foregoing properties can be achieved by a compositionthat consists essentially of a modified poly(1,4-butyleneterephthalate); a flame retardant phosphinate of the formula (Ia),(IIa), and/or a flame retardant polymer derived from formula (Ia) or(IIa); melamine polyphosphate and/or melamine cyanurate; a reinforcingflat glass fiber filler having a non-circular cross-section; and anoptional additive selected from the group consisting of a mold releaseagent, an antioxidant, a thermal stabilizer, an antioxidant, and a UVstabilizer. In particular, the foregoing composition achieves good flameretardancy for samples having a thickness of 0.4 and 0.8 mm, and goodimpact and tensile strength. Better high temperature molding stabilityand melt stability are also seen.

In an even more specific embodiment, the composition consistsessentially of, based on the total weight of the composition: from 20 to90 wt. % of a modified poly(butylene terephthalate) copolymer that (1)is derived from poly(ethylene terephthalate) component selected from thegroup consisting of poly(ethylene terephthalate) and poly(ethyleneterephthalate) copolymers and (2) that has at least one residue derivedfrom the poly(ethylene terephthalate) component; from 5 to 35 wt. % of aflame retardant phosphinate of the formula (Ia), a flame retardantdiphosphinate of the formula (IIa),[(R¹)(R²)(PO)—O]⁻ ₃Al³⁺  (Ia),[(O—POR¹)(R³)(POR²—O)]² ₃Al³⁺ ₂  (IIa),and/or a flame retardant polymer derived from formula (I) or (II),wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl,linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linearor branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁arylalkylene; from 1 to 25 wt. % of melamine polyphosphate and/ormelamine cyanurate; from 1 to 55 wt. % of a glass fiber having a flatcross-section; and from 0.1 to 5 wt. % of an additive selected from thegroup consisting of a mold release agent, an antioxidant, a thermalstabilizer, an antioxidant, and a UV stabilizer; wherein the componentshave a combined total weight of 100 wt. %, and wherein the at least oneresidue derived from the poly(ethylene terephthalate) componentcomprises mixtures of ethylene glycol and diethylene glycol groups andwherein a 0.8 mm thick molded sample comprising the composition has aUL-94 flammability rating of V0.

In a still more specific embodiment, the composition consistsessentially of, based on the total weight of the composition: from 20 to90 wt. % of a modified poly(butylene terephthalate) copolymer that (1)is derived from poly(ethylene terephthalate) component selected from thegroup consisting of poly(ethylene terephthalate) and poly(ethyleneterephthalate) copolymers and (2) that has at least one residue derivedfrom the poly(ethylene terephthalate) component; from 5 to 25 wt. % of aflame retardant phosphinate of the formula (Ia), a flame retardantdiphosphinate of the formula (IIa)[(R¹)(R²)(PO)—O]⁻ ₃Al³⁺  (Ia),[(O—POR¹)(R³)(POR²—O)]^(2↑) ₃Al³⁺ ₂  (IIa),and/or a flame retardant polymer derived from formula (I) or (II),wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl,linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linearor branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁arylalkylene; from 1 to 15 wt. % of melamine polyphosphate and/ormelamine cyanurate; from 1 to 45 wt. % of a glass fiber having a flatcross-section; and from 0.1 to 5 wt. % of an additive selected from thegroup consisting of a mold release agent, an antioxidant, a thermalstabilizer, an antioxidant, and a UV stabilizer; wherein the componentsand have a combined total weight of 100 wt. %; and wherein the at leastone residue derived from the poly(ethylene terephthalate) componentcomprises mixtures of ethylene glycol and diethylene glycol groupswherein the composition contains less than 900 ppm of a halogen selectedfrom the group consisting of bromine, chlorine, and combinationsthereof; and a 0.8 mm thick molded sample comprising the composition hasa UL-94 flammability rating of V0.

Also disclosed are molded articles comprising the composition, such aselectric and electronic parts, including, for example, connectors,circuit breakers, lamp holders, fusers, power distribution box,enclosures, and power plugs. A method of forming an article comprisesshaping by extruding, calendaring, or molding the composition to formthe article. Injection molded articles are specifically mentioned, forexample an injection molded connector. Other articles include fans,e.g., fans used in electronic devices such as computers.

It should be clear that the compositions and articles disclosed hereincan include reaction products of the above described components used informing the compositions and articles.

Advantageously, a molding composition containing the modifiedpoly(butylene terephthalate) copolymers can have a reduced CO₂ emissionsindex. The reduced CO₂ emissions index, as defined in this application,is the amount of CO₂, expressed in kg, that is saved when one (1) kg ofa composition containing the modified poly(butylene terephthalate)copolymers is made, as compared to the amount of CO₂, expressed in kg,that is created when the composition is made with poly(butyleneterephthalate) that is derived from monomers. Generally, ourcompositions generally have a reduced CO₂ emissions index that is morethan approximately 0.06 kg, and can range from 0.06 kg to 2.25 kg.

The basis for this feature is discussed below. The difference betweenthe amount of CO₂ that is created during ordinary processes for makingvirgin, monomer-derived PBT and the process for making 1 kg of themodified poly(butylene terephthalate) copolymers can range from 1.3 kgto 2.5 kg, or more suitably from 1.7 kg to 2.2 kg. It should be notedthat this difference is based on calculations for the entire processthat starts from crude oil to the monomers to the PBT versus scrap PETto oligomers to the modified PBT. In other words, the process for making1 kg of the modified poly(butylene terephthalate) copolymers creates 1.3to 2.5 kilograms less CO₂ as compared to the process for making 1 kg ofvirgin PBT from crude oil. To determine the ranges of the reduced CO₂emissions index for our compositions (which have the modified PBTcopolymers present in an amount ranging from 5 to 90 wt. %), the CO₂reduction index can be calculated by multiplying the lower amount of thepoly(butylene terephthalate) present in the composition, in percentageterms, with 1.3 (0.05×1.3=0.065) and the higher amount of thepoly(butylene terephthalate) times 2.5. (0.90×2.5=2.25).

These results can be derived and verified by using material and energybalance calculations (calculations that are well known in the chemicalengineering art) and comparing the amount of energy used to makemodified PBT copolymers from PET and the amount of energy used to makePBT from terephthalic acid.

Advantageously, our invention now provides previously unavailablebenefits. Our invention provides thermoplastic polyesters compositioncontaining modified polybutylene terephthalate copolymers made frompost-consumer or post-industrial PET, which having a combination ofdesirable flame retardance and mechanical properties. Our compositionscan further have useful mechanical properties, in particular impactstrength, tensile properties, and/or heat stability. The compositionscan optionally comprise a charring polymer, for example, apolyetherimide, to further improve mechanical strength and flameretardance. Such materials have many applications in the electronicsindustry.

The invention is further illustrated by the following non-limitingexamples.

EXAMPLES

The following materials in Table 1 were used in the examples thatfollow.

TABLE 1 Abbreviation Description Source VALOX IQ-PBT-1 intrinsicviscosity = 1.19 dl/g, weight-average SABIC Innovative Plastics Companymolecular weight = 110000 g/mol VALOX IQ-PBT-2 intrinsic viscosity =0.66 dl/g, weight-average SABIC Innovative Plastics Company molecularweight = 53400 g/mol Regular glass Standard 13 micron PBT glass (Glassfiber with PPG Industries round cross-section) Flat glass Flat glassfiber: cross section area equal to a Nitto Boseki round glass fiber witha diameter of 14 micrometers; flat ratio = 4; Fiber length = 3 mm MPPMelamine polyphosphate Ciba Specialty Al-DPA Aluminum diethyl phosphinicacid Clariant PEI Polyetherimide (ULTEM 1010) SABIC Innovative PlasticsCompany FR Brominated FR master batch SABIC Innovative Plastics CompanyTSAN SAN-encapsulated PTFE SABIC Innovative Plastics Company AO Hinderedphenol stabilizer Ciba Specialty PETS Pentaerythritol tetrastearate FaciSpA ZnP Zinc Phosphate Halox Pigments Talc ULTRATALC ™ 609 having amedian particle Barretts Minerals, Inc. size of less than 0.9 microns

Examples E1 to E2 and Comparative Examples C1 to C3

The purpose of these examples was to compare the performance ofcompositions of our invention containing flat glass fiber tocompositions containing regular glass fibers (fibers containing acircular cross section). The composition used in Examples E1 and E2exemplified an embodiment of our invention while compositions inExamples C1, C2, and C3 were used for comparison.

The ingredients as shown in Tables 2 to 4 were tumble blended and thenextruded on a 27 mm twin screw extruder with a vacuum vented mixingscrew, at a barrel and die head temperature between 240° C. and 265° C.and a screw speed of 300 rpm. The extrudate was cooled through a waterbath prior to pelletizing. ASTM Izod and flexural bars were injectionmolded on a van Dorn molding machine with a set temperature ofapproximately 240° C. to 265° C. The pellets were dried for 3 hours to 4hours at 120° C. in a forced air-circulating oven prior to injectionmolding.

Notched and un-notched Izod testing was performed on 75 mm×12.5 mm×3.2mm bars in accordance with ASTM D256. Bars were notched prior tomechanical property testing and were tested at 23° C. Flexuralproperties were measured in accordance with ASTM 790 on molded sampleshaving a thickness of 3.2 mm. Tensile properties were measured inaccordance with ASTM 790 on molded samples having a thickness of 3.2 mm.Heat deflection temperature was measured on molded samples having athickness of 3.2 mm in accordance with ASTM 648. Melt viscosity wasmeasured in accordance with ISO11443 at 250° C. Warpage was measured onmolded samples having a thickness of 1.6 mm in accordance with thefollowing method.

Warpage was measured on molded samples having a thickness of 1.6 mm inaccordance with the following method: (a) place the specimen on a flatsurface with the knockout pin or cavity dimension side up; (b) hold thecalibrated steel ruler in a vertical position behind the specimen; (c)while watching the ruler, press around the edge of the specimen andidentify the maximum distance from the flat surface. This is the warp ofthe specimen; (d) measure and record the specimen's warp to the nearestmillimeter.

Results are shown in Table 2.

TABLE 2 Unit E1 E2 C1 C2 C3 VALOX IQ PBT-1 % 25.82 23.32 26.23 25.8223.32 VALOX IQ PBT-2 % 25.82 23.32 26.23 25.82 23.32 Regular Glass % — —30 30 30 Flat Glass % 30 30 — — — MPP % 5 5 5 5 Al-DNP % 12.5 12.5 12.512.5 PEI % — 5 — 5 FR % — — 15.45 — — TSAN % 0.5 0.5 1.05 0.5 0.5 AO %0.15 0.15 0.04 0.15 0.15 PETS % 0.2 0.2 0.2 0.2 0.2 Zn—P % — — 0.3 — —Talc % — — 0.5 — — Total 100 100 100 100 100 Properties Melt Viscosityat 645 1/s shear Pa · s 328.7 376.8 250.7 346 401.2 Flexural Modulus MPa10300 11000 9410 10200 10500 Flexural Stress at Break MPa 173 182 177163 168 HDT ° C. 207.3 204.1 194.7 204 199.6 Notched IZOD Impact J/m70.4 76.4 61.6 56.4 50.9 Unnotched IZOD Impact J/m 644 626 612 497 487Modulus of Elasticity MPa 13100 14000 12000 13100 13100 Tensile Stressat Break MPa 104 101 102 99.8 95.8 Tensile Elongation at Break % 1.6 1.21.3 1.7 1.3 Warpage-As Molded mm 11 6.6 22 27 20 Warpage-Annealed mm 137.4 24 30 26 UL-94 at 0.80 mm V0 — — — —

The results in Table 2 demonstrate the advantages of flat glass as afiller, including improved the mechanical properties, flow, anddimensional stability, as compared to compositions comprising regularglass having a circular cross-section.

As shown in Table 2, C1 is a halogen FR, 30 wt % regular glass filledformulation, C2 is a non-halogenated FR, 30 wt % regular glassformulation, C3 is a non-halogenated FR, 30 wt % regular glass and 5 wt% Ultem-1010 (polyetherimide) formulation. E1 is a non-halogenated FR,30% flat glass filled formulation without Ultem-1010. E2 is anon-halogenated FR, 30% flat glass filled formulation with Ultem-1010.

The effects of flat glass fiber on mechanical properties, flow, anddimensional stability could be seen clearly from the comparison amongthe 5 examples. In non-halogenated FR formulations alone, by replacingregular glass (C2 and C3) with flat glass (E1 and E2), mechanicalproperties including notched and un-notched impact strength, tensilestrength, and flexural strength were improved by between 5 to 30%.Dimensional stability, expressed in warpage in this case, was alsoimproved by more than 100% with presence of flat glass fiber in theformulation (E1 and E2). Flat glass containing non-halogenated FRformula (E1 and E2) shows improvement in flow by 5%, as compared withboth regular glass fiber non-halogenated FR formulas (C2 and C3).

Flat glass fiber formulations with non-halogenated FR (E1 and E2) alsodisplayed comparable tensile strength and flexural stress or improvednotched and un-notched impacted strength, flexural modulus, HDT, anddimensional stability compared with the 30% regular glass filledhalogenated FR formulation (C1).

Examples E3 and C4 to C5

The purpose of these examples was to compare the performance ofcompositions of our invention containing flat glass fiber tocompositions containing regular glass fibers (fibers containing acircular cross section). The composition used in Example E3 exemplifiedan embodiment of our invention while compositions in Examples C4 and C5were used for comparison.

The formulation procedure of example E1 was followed using the materialsand quantities listed in Table 3, to form 25 wt. % glass filled flameretardant VALOX IQ PBT resins. Physical property testing results arealso shown in Table 3.

TABLE 3 Units E3 C4 C5 Component VALOX IQ PBT-1 % 25.825 28.73 25.825VALOX IQ PBT-2 % 25.825 28.73 25.825 Regular Glass % — 25 25 Flat Glass% 25 MPP % 5 5 Al-DNP % 12.5 12.5 PEI % 5 5 FR % — 15.45 — TSAN % 0.51.05 0.5 AO % 0.15 0.04 0.15 PETS % 0.2 0.2 0.2 Zn—P % — 0.3 — Talc % —0.5 — Total 100 100 100 Properties Melt Viscosity at 645 1/s Pa · s341.6 232.3 361.1 shear rate Flexural Modulus MPa 9450 8210 8800Flexural Stress at Break MPa 170 170 157 HDT ° C. 203.2 193.6 196.6Notched IZOD Impact J/m 67.6 58 49.3 Strength Unnotched IZOD Impact J/m536 615 517 Strength Modulus of Elasticity MPa 12100 11100 11000 TensileStress at Break MPa 100 109 97.5 Tensile Elongation at Break % 1.5 1.81.8 Warpage-As Molded mm 9.2 21 12 Warpage-Annealed mm 11 24 20

The results in Table 3 again demonstrate, improved mechanicalproperties, flow, and dimensional stability attributable to the flatglass filler.

As shown in Table 3, E3 is a non-halogenated FR, 25 wt. % flat glassfilled, and 5 wt. % PEI-filled formulation. C4 is a 25 wt. % glassfilled halogenated based FR formulation, and C5 is a non-halogenated FR,25 wt. % regular glass filled formulation with PEI.

In non-halogenated FR formulations, by replacing regular glass fiber(C5) with flat glass fiber (E3), mechanical properties including notchedand un-notched impact strength, and flexural strength were improved bybetween 4% to 30%. Dimensional stability, expressed in warpage in thiscase, was also improved by more than 30% with the presence of flat glassfiber in the formulation (E3). Flat glass containing non-halogenated FRformula (E3) shows improvement in flow by 6%, as compared with theregular glass fiber non-halogenated FR formula (C5).

The flat glass fiber, non-halogenated FR formulation (E3) has comparableflexural stress and improved un-notched impacted strength, flexuralmodulus, HDT, and dimensional stability compared with 25 wt. % regularglass filled halogen FR formulation (C4).

Examples E4 and C6 to C7

The purpose of these examples was to compare the performance ofcompositions of our invention containing flat glass fiber tocompositions containing regular glass fibers (fibers containing acircular cross section). The composition used in Example E4 exemplifiedan embodiment of our invention while compositions in Examples C6 and C7were used for comparison.

The formulation procedure for example E1 was followed using thematerials listed in Table 4 to form 15 wt. % glass filled flameretardant VALOX IQ PBT resins. As shown in Table 4, E4 is anon-halogenated FR, 15 wt. % flat glass filled formulation. C6 is a 15wt. % glass filled halogenated based FR formulation, and C7 is anon-halogenated FR, 15 wt. % regular glass filled formulation. Testingresults are also shown in Table 4.

TABLE 4 E4 C6 C7 VALOX IQ PBT 1 % 33.325 33.73 33.325 VALOX IQ PBT 2 %33.325 33.73 33.325 Regular Glass % — 15 15 Flat Glass % 15 — — MelaminePolyphosphate % 5 — 5 Aluminum diethyl Phosphinic % 12.5 12.5 acid PEI %— — — Brominated FR masterbatch % 15.45 SAN encapsulated PTFE % 0.5 1.050.5 Hindered phenol stabilizer % 0.15 0.04 0.15 Pentaerythritoltetrastearate % 0.2 0.2 0.2 Zinc Phosphate % — 0.3 — Ultratalc % — 0.5 —Formulation Total 100 100 100 Properties Melt Viscosity at 645 1/s Pa ·s 246.9 198.7 274 shear rate Flexural Modulus MPa 6730 5750 6390Flexural Stress at Break MPa 139 141 131 HDT ° C. 200.1 184.5 192.2Notched IZOD Impact J/m 54.5 40.2 39.4 Strength Unnotched IZOD ImpactJ/m 390 255 305 Strength Modulus of Elasticity MPa 8580 7360 8440Tensile Stress at Break MPa 85.2 86.2 81.9 Tensile Elongation at Break %2.2 1.9 2.4 Warpage-As molded mm 15 19 20 Warpage-Annealed Mm 18 21 22

The results in Table 4 show that the use of flat glass filler at a 15wt. % level also improved the mechanical properties, flow, anddimensional stability, as compared to compositions comprising regularglass having a circular cross-section.

In the non-halogenated FR formulations, replacing regular glass fiber(C7) with flat glass fiber (E4), mechanical properties were improved by4% to 38%, including notched and un-notched impact strength, flexuralstrength, tensile strength, and HDT. Dimensional stability, expressed inwarpage in this case, was also improved by about 20% with the presenceof flat glass fiber in the formulation (E4). The flat glass,non-halogenated FR formula (E4) also shows improvement in flow by 10%over the regular glass fiber non-halogenated FR formulation C7. The flatglass fiber non-halogenated FR formulation (E4) also displayedcomparable flexural strength and tensile strength, and improvedun-notched and notched impacted strength, flexural modulus, HDT, anddimensional stability, compared with the 15 wt. % glass filled halogenFR formulation (C6).

While the invention has been described with reference to a preferredembodiment, it will be understood by those skilled in the art thatvarious changes can be made and equivalents can be substituted forelements thereof without departing from the scope of the invention. Inaddition, many modifications can be made to adapt a particular situationor material to the teachings of the invention without departing fromessential scope thereof. Therefore, it is intended that the inventionnot be limited to the particular embodiment disclosed as the best modecontemplated for carrying out this invention, but that the inventionwill include all embodiments falling within the scope of the appendedclaims.

What is claimed is:
 1. A composition comprising, based on the total weight of the composition: from 20 to 90 wt. % of a polyester component comprising a modified poly(butylene terephthalate) copolymer, that (1) is derived from a poly(ethylene terephthalate) copolymer and (2) that has at least one residue derived from the poly(ethylene terephthalate) copolymer; from 5 to 35 wt. % of a flame retardant phosphinate of the formula (I) [(R¹)(R²)(PO)—O]⁻ _(m)M^(m+)  (I) a flame retardant diphosphinate of the formula (II) [(O—POR¹)(R³)(POR²—O)]²⁻ _(n)M^(m+) _(x)  (II), and/or a flame retardant polymer derived from the flame retardant phosphinate of the formula (I) or the flame retardant diphosphinate of the formula (II), wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl, linear or branched, or C₆-C₁₀ aryl; M is an alkaline earth metal, alkali metal, Al, Ti, Zn, Fe, or boron; m is 1, 2, 3 or 4; n is 1, 2, or 3; and x is 1 or 2; from 1 to 25 wt. % of a melamine polyphosphate, melamine cyanurate, melamine pyrophosphate, and/or melamine phosphate; from greater than zero to 50 wt. % of a glass fiber having a non-circular cross-section; and from 0 to 5 wt. % of an additive selected from the group consisting of a mold release agent, an antioxidant, a thermal stabilizer, and a UV stabilizer; wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer comprises mixtures of ethylene glycol and diethylene glycol groups; and wherein a molded article comprising the composition has an unnotched Izod impact strength at least 20% higher than for the same composition having the same amount of circular glass fibers, each measured at 23° C. in accordance with ASTM D256.
 2. The composition of claim 1, wherein a molded article comprising the composition has an unnotched Izod impact strength from 300 to 700 J/m, measured at 23° C. in accordance with ASTM D256.
 3. The composition of claim 1, wherein a molded article comprising the composition has a notched Izod impact strength from 50 to 80 J/m, measured at 23° C. in accordance with ASTM D256.
 4. The composition of claim 1, wherein a molded article comprising the composition has a notched Izod impact strength at least 3% higher than for the same composition having the same amount of circular glass fibers, each measured at 23° C. in accordance with ASTM D256.
 5. The composition of claim 1, wherein a molded article comprising the composition has a tensile modulus of elasticity from 2000 MPa to 15000 MPa, measured in accordance with ASTM
 790. 6. The composition of claim 1, wherein a molded article comprising the composition has a tensile stress at break from 80 to 150 MPa, measured in accordance with ASTM
 790. 7. The composition of claim 1, wherein a molded article comprising the composition has a flexural modulus of 3000 MPa to 20000 MPa, measured in accordance with ASTM
 790. 8. The composition of claim 1, wherein a molded article comprising the composition has a heat deflection temperature of from 195° C. to 230° C., measured in accordance with ASTM D648 at 1.82 MPa.
 9. The composition of claim 1, wherein a 0.80 mm thick molded sample comprising the composition has a UL-94 flammability rating of V0.
 10. The composition of claim 1, wherein a molded article comprising the composition has a melting viscosity of from 200 to 400 Pa·s, measured in accordance with ISO11443 at 250° C. and a shear rate of 645 1/s.
 11. The composition of claim 1, wherein a molded article comprising the composition has a melting viscosity at least 5% lower than for the same composition having the same amount of circular glass fibers, each measured at 250° C. in accordance with ISO11443.
 12. The composition of claim 1, wherein a molded article comprising the composition has a warpage of from 5 to 20 mm, measured at 23° C. as molded.
 13. The composition of claim 1, wherein the composition contains less than 900 ppm of a halogen selected from the group consisting of bromine, chlorine, and combinations thereof.
 14. The composition of claim 1, wherein a molded article comprising the composition has a warpage at least 20% lower than for the same composition having the same amount of circular glass fibers, each measured at 23° C. as molded.
 15. The composition of claim 1, wherein a molded article comprising the composition has a warpage of from 5 to 20 mm, measured after annealed at 70° C. for 48 Hrs.
 16. The composition of claim 1, wherein a molded article comprising the composition has a warpage at least 15% lower than for the same composition having the same amount of circular glass fibers, each measured after annealed at 70° C. for 48 Hrs.
 17. The composition of claim 1, wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer further comprises a member selected from the group consisting of isophthalic acid groups, antimony-containing compounds, germanium-containing compounds, titanium-containing compounds, cobalt-containing compounds, tin-containing compounds, aluminum, aluminum salts, 1,3-cyclohexane dimethanol isomers, 1,4-cyclohexane dimethanol isomers, alkaline earth metal salts, alkali salts, phosphorous-containing compounds and anions, sulfur-containing compounds and anions, naphthalene dicarboxylic acids, 1,3-propane diol groups, and combinations thereof.
 18. The composition of claim 1, wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer further comprises isophthalic acid groups.
 19. The composition of claim 1, wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer further comprises cobalt-containing compounds.
 20. The composition of claim 19, wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer further comprises isophthalic acid groups.
 21. The composition of claim 2, wherein the modified poly(butylene terephthalate) copolymer is derived from a 1,4-butanediol that is derived from biomass.
 22. The composition of claim 2, wherein the polyester component further comprises virgin poly(1,4-butylene terephthalate).
 23. The composition of claim 1, wherein the polyester component further comprises a second polyester selected from the group consisting of poly(ethylene terephthalate), poly(1,4-butylene terephthalate), poly(ethylene naphthalate), poly(1,4-butylene naphthalate), (polytrimethylene terephthalate), poly(1,4-cyclohexanedimethylene, 1,4-cyclohexanedicarboxylate), poly(1,4-cyclohexanedimethylene terephthalate), poly(1,4-butylene-co-1,4-but-2-ene diol terephthalate), poly(cyclohexanedimethylene-co-ethylene terephthalate), and a combination thereof.
 24. The composition of claim 23, wherein the second polyester is virgin poly(1,4-butylene terephthalate).
 25. The composition of claim 1, wherein the glass fiber has a trapezoidal cross section.
 26. The composition of claim 1, wherein the glass fiber has a rectangular cross-section.
 27. The composition of claim 1, wherein the glass fiber has a square cross-section.
 28. The composition of claim 1, wherein the glass fiber has an average aspect ratio of 2 to
 5. 29. The composition of claim 1, wherein the glass fibers have an average length of 0.1 mm to 10 mm.
 30. The composition of claim 1, wherein M is selected from the group consisting of magnesium, calcium, aluminum, zinc, and a combination thereof.
 31. The composition of claim 1, wherein M is aluminum.
 32. The composition of claim 1, wherein the flame retardant phosphinate of the formula (I) or of the formula (II) comprises an aluminum phosphinate.
 33. The composition of claim 1, wherein the composition comprises no polyetherimide.
 34. The composition of claim 1, wherein the composition comprises more than 0 to less than 10 wt % of a polyetherimide, based on the total weight of the composition.
 35. The composition of claim 1, wherein the composition comprises an antidrip agent.
 36. The composition of claim 1, wherein the composition further comprises an additive selected from the group consisting of a lubricant, a quencher, a plasticizer, an antistatic agent, a dye, a pigment, a laser marking additive, a radiation stabilizer, and a combination thereof.
 37. The composition of claim 1, wherein the composition comprises from more than 0 to less than 5 wt. % of a chlorinated organic compound and/or a brominated organic compound.
 38. A composition consisting essentially of, based on the total weight of the composition: from 20 to 90 wt. % of a modified poly(butylene terephthalate) copolymer that (1) is derived from a poly(ethylene terephthalate) copolymer and (2) that has at least one residue derived from the poly(ethylene terephthalate) copolymer; from 5 to 35 wt. % of a flame retardant phosphinate of the formula (Ia) [(R¹)(R²)(PO)—O]⁻ ₃Al³⁺  (Ia), a flame retardant diphosphinate of the formula (IIa) [(O—POR¹)(R³)(POR²—O)]²⁻ ₃Al³⁺ ₂(IIa), and/or a flame retardant polymer derived from formula (I) or (II), wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl, linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linear or branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁ arylalkylene; from 1 to 25 wt. % of melamine polyphosphate and/or melamine cyanurate; from greater than 0 to 50 wt. % of a glass fiber having a flat cross-section; and from 0 to 5 wt. % of an additive selected from the group consisting of a mold release agent, an antioxidant, a thermal stabilizer, and a UV stabilizer; wherein the composition contains less than 900 ppm of a halogen selected from the group consisting of bromine, chlorine, and combinations thereof; wherein the components have a combined total weight of 100 wt. %, wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer comprises mixtures of ethylene glycol and diethylene glycol groups; and wherein a 0.8 mm thick molded sample comprising the composition has a UL-94 flammability rating of V0; and wherein a molded article comprising the composition has an unnotched Izod impact strength at least 20% higher than for the same composition having the same amount of circular glass fibers, each measured at 23° C. in accordance with ASTM D256.
 39. A composition consisting essentially of, based on the total weight of the composition: from 20 to 90 wt. % of a modified poly(butylene terephthalate) copolymer that (1) is derived from a poly(ethylene terephthalate) copolymer and (2) that has at least one residue derived from the poly(ethylene terephthalate) copolymer; from 5 to 25 wt. % of a flame retardant phosphinate of the formula (Ia) [(R¹)(R²)(PO)—O]⁻ ₃Al³⁺  (Ia), a flame retardant diphosphinate of the formula (IIa) [(O—POR¹)(R³)(POR²—O)]²⁻ ₃Al³⁺ ₂  (IIa), and/or a flame retardant polymer derived from formula (I) or (II), wherein R¹ and R² are identical or different and are H, C₁-C₆ alkyl, linear or branched, or C₆-C₁₀ aryl; and R³ is C₁-C₁₀, alkylene, linear or branched, C₆-C₁₀ arylene, C₇-C₁₁ alkylarylene, or C₇-C₁₁ arylalkylene; from 1 to 15 wt. % of melamine polyphosphate and/or melamine cyanurate; from greater than 0 to 45 wt. % of a glass fiber having a flat cross-section; and from 0 to 5 wt. % of an additive selected from the group consisting of a mold release agent, an antioxidant, a thermal stabilizer, and a UV stabilizer; wherein the components have a combined total weight of 100 wt. %; and wherein the at least one residue derived from the poly(ethylene terephthalate) copolymer comprises mixtures of ethylene glycol and diethylene glycol groups; wherein the composition contains less than 900 ppm of a halogen selected from the group consisting of bromine, chlorine, and combinations thereof; and wherein a 0.8 mm thick molded sample comprising the composition has a UL-94 flammability rating of V0; and wherein a molded article comprising the composition has an unnotched Izod impact strength at least 20% higher than for the same composition having the same amount of circular glass fibers, each measured at 23° C. in accordance with ASTM D256.
 40. A method for the manufacture of a composition, comprising blending the components of the composition of claim
 1. 41. An article comprising the composition of claim
 1. 42. The article of claim 41, wherein the article is an injection molded article.
 43. A method of forming an article comprising shaping by extruding, calendaring, or molding the composition of claim 1 to form the article.
 44. The composition of claim 1, wherein the ethylene glycol groups are present in an amount from 0.1 to 10 mole %, based on the total moles of diol in the modified poly(butylene terephthalate) copolymer.
 45. The composition of claim 1, wherein the diethylene glycol groups are present in an amount from 0.1 to 10 mole %, based on the total moles of diol in the modified poly(butylene terephthalate) copolymer.
 46. The composition of claim 18, wherein the isophthalic acid groups are present in an amount from 0.1 to 10 mole %, based on the total moles of diacid/diester in the modified poly(butylene terephthalate) copolymer.
 47. The composition of claim 18, wherein the ethylene glycol groups, diethylene glycol groups, and isophthalic acid groups are present in an amount from more than 0 to less than or equal to 23 equivalents, relative to the total of 100 equivalents of diol groups and 100 equivalents of diacid groups in the modified poly(butylene terephthalate) copolymer.
 48. The composition of claim 21, wherein the biomass is selected from the group consisting of grains and cellulosic materials.
 49. The composition of claim 1, wherein the modified poly(butylene terephthalate) copolymer has a CO₂ reduction index of 1.3 to 2.5 kg. 